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Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada



Karina Chevil , Abdoulmajid Eslami, Weixing Chen, and Reg Eadie, Department of Chemical and Materials Engineering, University of Alberta Edmonton, Canada T6G 2G6 1 Contact Author Richard Kania, TransCanada Pipelines Limited Calgary, Alberta, Canada T2P 5H1 Robert Worthingham Worthingham Professional Services Inc. Calgary, Alberta, Canada T2L 2E5 2 Formerly at TransCanada Pipelines Limited Greg Van Boven Spectra Energy Transmission Vancouver, British Columbia, Canada V6E 3P3
2 1

ABSTRACT Coating disbondment on pipelines is a common phenomenon that leads to exposure of the pipeline metal to ground water solutions, promoting a corrosive environment which is associated with stress corrosion cracking (SCC). This investigation tracks the corrosion behavior of X-65 steel at different coating disbondments at Open Circuit Potential (OCP) conditions through weight loss tests, as well as SEM analysis. For the weight loss test, X-65 coupons were placed into a vertical coupon holder with varying gap sizes between the coupons and the shielding (2 mm 5 mm, and 10 mm) simulating the coating disbondment. The results of the tests suggest that the corrosion rate inside the gap is dependent on the mass transfer rate of CO2. For larger gaps, the corrosion rate inside the gap decreases almost linearly with position (highest at the top of the disbondment) and is dependent on the iron carbonate film deposition. For smaller gaps (5 mm) a galvanic effect was observed between the coupons at the top of the disbondment (anodic) which showed a high degree of general corrosion, and the coupons at the bottom of the disbondment (cathodic) which had very low corrosion rates. The experimental observations

were related to the corrosion scenarios found in the field. Cathodic protection strategies with respect to the geometry of disbondment are also discussed. INTRODUCTION Underground pipelines are protected from environmental corrosion through protective coating of the pipeline and the application of cathodic protection (CP). Two of the common coatings used on many existing buried pipelines for those purposes are poly-ethylene and epoxy coatings. Once a coating disbondment occurs, ground water solutions may enter the gap between the membrane and the steel, and create an electrochemical environment that will affect the integrity of the steel through different types of corrosion and stress corrosion cracking (SCC). A coating disbondment may exist on the pipe prior to its placement in the field due to inadequate coating (e.g. poor adhesion to a pipe surface) or a crevice which is related to the geometry of the wrapped coating, such as tenting that results from spiral-wrapped coating tapes that overlap in the helix line or ridges between the pipe surface and the tape at welds. It can also develop on the pipeline during its operation as

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a result of soil stresses or cathodic reduction in bonding due to excessive CP [1, 2]. SCC is believed to be initiated and developed under the synergistic effect of stress, material, and environment [1,3], Two forms of SCC have been previously identified in pipeline steel in terms of the observed crack morphologies: intergranular and transgranular. Intergranular cracks are narrow and tight cracks that initiate and propagate along grain boundaries. They are associated with high pH concentrated carbonate-bicarbonate solutions (8.5-10.5) in contact with the steel. In transgranular SCC, cracks are usually wide and propagate through grains. Transgranular SCC is commonly referred to as Near Neutral pH Stress Corrosion Cracking (NNpHSCC), which occurs in dilute bicarbonate solutions with a near neutral pH (5.5-7.5) [5]. Studies have shown that localized corrosion sites such as pits and crevices act as stress raisers at which cracks initiate in various environments [5, 6]. It is, however, still debatable whether NNpHSCC is controlled by stress intensification or specific electrochemical conditions at these localized corrosion sites. X-65 pipeline steel has shown susceptibility to NNpHSCC in field studies and laboratory simulations [7]. Numerous studies have been performed to study the effect of CP on the electrochemical conditions, pit initiation and corrosion rate of those steels. The experiments of Chen et al. showed that in the early stages of the steel corrosion inside a disbonded coating, CP protection is not effective due to the fact that it cannot reach the bottom of the disbondment; oxygen depletion inside the crevice promotes a separation of anodic (crevice) and cathodic (holiday) sites which causes the corrosion of the steel inside the disbondment [8]. The Perdomo experiments, on the other hand, concluded that a CP current flow into the crevice is not a necessary condition for the steel protection, since corrosion protection in the crevice is a result of CP-induced chemical modifications (oxygen consumption and increase in alkalinity) [9]. The experiments mentioned above were performed in aerobic conditions; however, SCC occurring on pipeline steel under disbonded coatings tends to be anaerobic. Eslami et al. investigated the conditions inside a disbondment with an application of CP in anaerobic conditions. They showed that with an application of CP, pitting was most severe at the middle of the disbondment with insufficient amounts of CP, while regions without any CP showed the highest degree of general corrosion [10]. In many cases, results of field studies and laboratory experiments demonstrated that despite the application of CP to

the pipeline, shielding coatings such as polyethylene, with electrically insulating properties limit the penetration of CP into the disbondment [11, 12]. This effect is enhanced by the high resistivity of certain types of ground water that form a barrier to CP penetration [10]. Despite the wide study of the electrochemical conditions underneath disbonded coatings, little information has been provided regarding the corrosion rate in these conditions, and the effect of the gap size on the corrosion rate at the different positions inside the disbondment and at the Open Mouth (OM). The objective of this experiment was to study the corrosion rate of X-65 steel under different gap sizes between the disbondment coating and the steel surface at different positions from the OM where ground water has entered into the disbonded holiday in the absence of CP. The experiment was performed with the absence of oxygen, replicating the conditions of an anaerobic soil site. This experiment aimed to study the corrosion rate of X-65 steel at the initiation stage; therefore, non-pre-cracked specimens were used to quantify the corrosion behavior of the steel through weight loss calculations. EXPERIMENTAL Setup In the experiments, Poly Methyl Methacrylate (PMMA) corrosion cells containing a vertical coupon holder were used; the assembly is shown in Fig 1. The design of the cell included a gas inlet and outlet, as well as an opening at the top with a removable plug to collect small-volume solution samples.


The coupon holder, shown in Fig 2, is comprised of a solid PMMA back, a PMMA part with seven square openings, and a

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shielding plate with an opening at the top. The gap between the coupon holder and the shielding plate varied from 1 cm to 2 mm, simulating various size disbondments. The shielding material used in this experiment was made out of PMMA, which was proven to have similar gas permeability as polyethylene tape coatings used in the field. Due to the low gas permeability of the PMMA shielding, the gas entrance to the disbondement is restricted to the OM.

continuously purged with a mixture of 5%CO2-N2 which was released from the bottom. The test was performed at Open Circuit Potential (OCP), without an application of CP current. The duration of the test was 30 days, after which the specimens were taken out of the solution, quickly dried, cleaned with ethanol, and weighed. The duration of the test was chosen based on the results of a previous experiment [13] that lasted for 25 days, where the weight loss rate of X-65 coupons in a C2 solution was constant after a period shorter than 5 days. The corrosion rate of each coupon was calculated based on its weight loss, using Equation 1.


W2 and W1 are the initial and final weights, respectfully; t is the time, is the density of the metal, and A is the area of the coupon exposed to the solution. At the end of the test, the pH inside the gap at three distinct locations (OM, middle, bottom) was measured using commercial micro-electrodes. The diameter of the microelectrodes was smaller than 1.6 mm; they were calibrated carefully in buffer solutions of pH 4 and 7 prior to each measurement. As well, the conductivity of the solution inside the shielding and outside the shielding was measured with the use of the Accumet XL60 Dual Channel Meter. The calibration of the conductivity probe was performed with a Conductivity Standard Solution of the Fisher brand. Characterization Scanning Electron Microscopy (SEM) analysis was performed to explore the corrosion effect on the surface of the specimens at different positions from the OM of the disbondment. For the SEM characterization, the samples were immersed in an ultrasonic bath with a rust solution for a duration of 2 minutes. The chemical composition of the rust-removing solution is presented in Table 3. RESULTS Weight Loss Test Results The corrosion rate of the pipeline steel at different positions from the OM in Test A is shown in Fig 3. From Fig 3 it can be seen that the corrosion rate in the test without the shielding is constant at all the coupon positions inside the disbondment. In the case of a gap size of 10 mm, the corrosion rate is the highest at the OM, and decreases almost linearly as the distance from the OM increases. For the test with the 5 mm gap distance, the corrosion rate at the OM is higher than the corrosion rate of the


To analyze the effect of the coating disbondment size on the corrosion rate, four scenarios were tested: no shielding, 1 cm gap distance (large disbondment), 5 mm gap distance, and 2 mm gap distance. In each experiment, seven X-65 square specimens with a 1.9 cm side were used. Repeats of these tests were also performed to confirm the observations. The chemical composition of X-65 pipeline steel is presented in Table 1. The specimens were machined from sections of X-65 pipeline steel from pipes taken from the field. The specimens were ground to 600 grit, immersed into an ethanol ultrasonic bath for 2 minutes and quickly dried. After the specimens initial weight was recorded, they were placed in a vertical coupon holder attached to the shielding plate with acetal rods. C2 solution simulating the underground soil solution found in the areas where SCC corrosion had occurred was used as the electrolyte in the corrosion cell [13]. The C2 solution chemistry is presented in Table 2. The solution was purged with 5% CO2N2 for at least 48 hours prior to testing while its pH reached a stable value of 6.29. In the mentioned assembly, only one face of each specimen was exposed to the solution in the gap (exposed area 1.96 cm2). The specimen at the top of the coupon holder was outside of the gap, simulating the part of the pipe positioned at the OM of the disbondment. The corrosion cell was properly sealed to avoid oxygen penetration, and

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tests without a shielding and the large gap; however, it is lower than the corrosion rate at the test with the 2 mm gap shielding.



Electrochemical Conditions The measured range of the pH at the different positions inside the shielding was at the neutral pH region (between 6 and 7), indicating that no high pH environment was formed. This demonstrates that the observed variation in the corrosion rate is most likely not associated with the formation of a passive film on the surface of the coupons typical to alkaline environments. The exact pH values need to be confirmed.

SEM Characterization At the end of each test, SEM analysis was performed on the coupons. The SEM results of the 5 mm gap size are presented in Fig. 4. The OM has experienced severe general corrosion with some deep pits occasionally observed. Both the middle and bottom section suffered little corrosion, as evidence with the retention of scratches made during sample preparation prior to corrosion exposure. At these locations, only some small pits were found on the surface, which were mainly caused by dissolution of inclusions on the surface. Similar results were obtained for the 2 mm gap size; however, the pitting on the coupon at the bottom of the 2 mm gap size appeared to be less severe compared to the 5 mm gap size, as shown in Fig. 5. DISCUSSION In the present system X-65 coupons were placed inside disbondments of different sizes in a vertical orientation. The gravitational effect in those systems was not considered due to the fact that no corrosion product formed during the experiment.




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The pH of the C2 solution after purging for two days was approximately 6.29. Continuous purging with CO2 generates carbonic acid through the carbon dioxide hydration reaction (Reaction 1) [5]. CO2 + H2O H2CO3 (1)

Small Gap Disbondments (2 mm and 5 mm Gap Distance) For smaller gap sizes, the following two corrosion senarios have been identified: 1) Higher corrosion rate of the coupon at the OM compared to the corrosion rate of the coupons inside the shielding: The corrosion of the pipeline steel in near neutral pH aqueous solution is primarily related to acidic condition of the solution. It has been well established that the rate of general corrosion of pipeline steel exposed to near neutral pH environments can be correlated to the pH of the solutions [13]. For the aqueous solution with the same chemical composition, the corrosion rate can be correlated to the CO2 level in the environment. As a result, the decreased corrosion rate toward the bottom of the disbonded coating should be caused by the chemical gradient of CO2 related species as described in Reactions 1 to 3. 2) Higher corrosion rate at the OM with the decreasing gap distance of the disbondment: First of all, this observation should not be a result of crevice corrosion. For the latter mechanism, severe corrosion is usually seen inside the crevice, that is, within the disbonded area in the present situation, which is obviously not true. It is believed that there is a galvanic cell, where the bottom coupons act as cathodic sites and the top coupons act as anodic sites where a high degree of steel dissolution occurs, has been established and is responsible for the enhanced corrosion at the OM when the disbondment gap was very small. This galvanic cell, is obviously a concentration cell, which might be caused by different rate of ionic diffusion within the disbondment, for example, fast diffusion of H+ toward the bottom of disbondment where the steel surface serves as a cathode for the reduction of H+ (Reaction 5), while the

The formed carbonic acid further dissociates into bicarbonate (Reaction 2) and carbonate (Reaction 3) in a two step process: H2CO3 H+ + HCO3HCO3- H+ + CO32(2) (3)

Simultaneously, steel oxidation (Reaction 4), and hydrogen reduction (Reaction 5) occur. Fe Fe+2+2e 2H++2e 2H (4) (5)

Weight Loss Analysis Based on the results obtained by the weight loss test, a plot of the corrosion rate at the OM at various gap distances was obtained and is presented in Fig 6. From Fig 6 it can be seen that the corrosion rate decreases with gaps from 2 mm to 10 mm, and slightly increases as the gap increases beyond 10 mm. The variation of the corrosion rate with gap size demonstrates the possibility of two different mechanisms governing the corrosion behavior in each system.

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OM allows more CO2 dissociation (Reation 2 and 3) and dissolution of Fe (Rection 4). The exact mechanism of this galvanic effect is not well understood yet, and will require additional electrochemical data and tests.

Large Gap Disbondment (10 mm Gap Distance) The results of the 10 mm gap exhibit an almost linear decrease in the corrosion rate as the distance from the OM increases. From these results it can be speculated that there exists a CO2 concentration gradient inside the gap affected by the mass transfer rate of CO2 into the disbondment. The geometry of the disbondment allowed the entrance of the solution into the shielding only from the narrow opening at the top, which limited the diffusion of CO2 into the shielding. Since the gap is relatively large, CO2 was able to penetrate inside the 10 mm gap shielding; a gradient in the CO2 concentration results in a gradient of carbonate and bicarbonate ions through reactions 2 and 3 which may have affected the potential of the steel at the different positions or resulted in a formation of a protective film of different thicknesses on the surface of the coupons. It has been previously observed that iron carbonate films form on the steel surface during corrosion of steel in CO2 systems when the concentration of Fe2+ and CO32- in the aqueous solution exceeds the solubility limit (Reaction 6)[12, 14]. Fe2+ + CO32- FeCO3 (6) Concentration gradients of carbonate molecules may result in variations in the deposition rate of the film onto the surface of the coupons at the different positions. The formation of the film is dependent on the pH inside the disbondment since the concentration of CO32- varies with pH; it should be noted that depending on the system, the CO32- concentration can be relatively high in a near-neutral pH range [15]. Chen explained the reduction of the surface area due to a formation of a FeCO 3 film on the surface as a factor that decreases the corrosion rate [12]. Additional experiments are required to validate this assumption in reference to the systems described in this paper. For larger gap sizes, the concentration gradient of CO2 inside the disbondment decreases, which also decreases the corrosion rate differences between the coupons at various positions. An extreme case of this scenario is demonstrated with an infinite gap size where the shielding was removed. In this system the release of the CO2 gas was made from the bottom and its dissolution was uniform; therefore, the CO2 concentration was equal at all the coupon position. In those conditions, the corrosion rate of the coupons in all the positions was constant. SEM Characterization The coupon at the OM and the coupon at position 0 exhibits pitting and general corrosion, which is consistent with the high

corrosion rates obtained by the weight loss test. The coupons inside the shielding demonstrate pitting with numerous submicrometer pits with circular shapes. The presence of grinding scratches on the surface of the coupons inside the shielding indicates that they did not experience severe general corrosion. The experimental results show that pitting was most severe at positions away from the OM. A proposed mechanism for the pit formation is the dissolution of sub-micrometer constituents prior to the increase in the pH of the solution inside the shielding [5]. This dissolution may have occurred at the coupons at the OM as well, but would not be observed due to the high rate of general corrosion at these locations. The main features of the 2 mm gap SEM images were similar to the ones observed on the SEM images of the 5 mm gap experiment, namely, a large degree of general corrosion at the OM and adjacent locations, and still observable scratch marks and small pits at the bottom of the disbondment. When comparing the SEM results of the 5 mm gap and the 2 mm gap it can be seen that the pit size and amount at the bottom of the disbondment of the 2 mm gap is greater than at the 5 mm gap. Since pitting is likely related to dissolution of non-metallic micro-constituents in the lattice, the difference in the amount of pits between the two tests might suggest an effect of CO2 concentration on the pitting. To confirm this, further test are required. Field Observations The results obtained from the current study may be related to several scenarios of SCC often found in the field. The experiments in this study were performed under OCP conditions; nonetheless, the bridge between the field findings and the current experimental observations may shed new light on the development of practical strategies for mitigating the occurrence of SCC in the field with CP. 1) Accelerated general corrosion: severe general corrosion can be often found on the pipe surface. It may be present at the location next to a SCC colony or sometimes at the location with SCC where general corrosion gradually destroyed the progress of cracking. It is generally believed that the pipe surface with severe corrosion is located within the disbonded area, especially toward the bottom of disbondment where CP current cannot reach. This research indicates that severe corrosion could occur at the OM provided that CP is not present and the disbondment gap is small. On the other hand, general corrosion toward the bottom of disbondment could occur only when the disbondment gap is large regardless whether CP is applied or not. This observation may also explain the different susceptibility of PE tape coated pipeline steels compared to asphalt coated pipeline. The latter tends to create narrower disbonding gap and corrosion may

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occur only at the OM and when CP is not applied. The former is more susceptible to corrosion cracking, as found in the field, because large disbonding gaps are present and corrosion can occur with and without CP protection. 2) Strategies of Cathodic Protection: Increasing CP current penetration into the disbonded area has been an effort to minimize corrosion and stress corrosion cracking of pipeline steels. From the experimental simulation performed in this study, such an effort might yield a positive result only when the disbonded gap is large. For coatings that will generate a narrow gap, it is essential that CP is constantly applied so that enhanced corrosion at the OM of disbondment can be prevented. For coatings that will lead to a large disbonded gap, increasing CP penetration may yield some benefit only for those coatings with large disbonded gaps. But the benefit would be limited if the disbondment is also deep. These assumptions would need to be confirmed by a follow-up study. The findings may also provide some insights on the development of new coating materials. It is believed that a coating material that can be fractured into short fragments after being damaged could be protected more effectively by CP. 3) Narrowing of disbondment gap in the field: the experimental results, in particular the results of the small gap, can be relevant to a situation where the gap starts off large at the top and gradually narrows down. This situation needs to be explored in depth in future experiments. CONCLUSION The experiment analyzed the corrosion rate of X-65 steel at different positions from non-permeable shielding disbondments for different gap sizes generated by the disbondment. The experiment simulated anaerobic conditions inside the disbondment with a continuous supply of CO2 in the absence of any cathodic protection. It was found that both for larger (>10 mm) and smaller (2 mm, 5 mm) disbondment sizes the corrosion rate of the steel at the OM of the disbondment is the highest compared to the corrosion rate inside the disbondment. For smaller disbondment sizes (2 mm and 5 mm), the CO2 gradient, generated by the geometry of the gap, produces a galvanic effect between the steel inside the disbondment (cathodic site) and the steel outside the disbondment (anodic site). For larger disbondment sizes (10 mm) the corrosion rate of the steel inside the disbondment decreased almost linearly with position inside the gap, and was likely related to the CO2 gradient as well; however, no galvanic effect was generated between the coupons at the bottom of the gap and the OM. The

observations seem consistent with the field findings. It is suggested based on the experimental findings that cathodic protection should be provided based on the type of coatings and their geometry of disbondment. ACKNOWLEDGMENTS The authors would like to thank US Department of Transportation, Natural Science and Engineering Research Council of Canada, TransCanada Pipelines Limited and Spectra Energy for financial support. REFERENCES 1. Baker, M. Stress Corrosion Cracking Study- Final Report. pp 48. January 2005. 2. Sridhar, N, Dunn, D.S., and Seth, M. Application of a General Reactive Transport Model to Predict Environment under Disbonded Coatings. Corrosion, 2000. NACE International, Houston, TX (366). 3. Fang, B.Y., Atrens, A, Wang, J.Q., Han, E.H., Zhu, Z.Y., and Ke. W.J. Review of Stress Corrosion Cracking of Pipeline Steels in Low and High pH Solutions. Mater. Sci, 2003. 200 38, pp. 127132. 4. National Energy Board. Stress Corrosion Cracking on Canadian oil and Gas Pipelines. MH-2-95, National Energy Board (Calgary, Alberta, 1996). 5. Elboujdaini, M. and Revie. R. W. Metallurgical Factors in Stress Corrosion Cracking (SCC) and Hydrogen-induced Cracking (HIC). J Solid State Electrochem, 2009. 13, pp. 10911099. 6. Turnbull, A., McCartney L.N., Zhou S. A Model to Predict the Evolution of Pitting Corrosion and the Pitto-crack Transition Incorporating Statically Distributed Input Parameters. Proceedings of the Second International Conference on Environment Induced Cracking of Metals (EICM-2), 2004. Alberta, Canada 7. Chen W., Kania. R., Worthingham. R., and Van Boven G. Transgranular Crack Growth in Pipeline Steels Exposed to Near-neutral pH Soil Aqueous Solutions: the Role of Hydrogen. Acta Materialia, 2009. 57 pp. 6200-6214. 8. Chen, X., Li, X.G., Du, C.W., Cheng. Y.F. Effect of Cathodic Protection on Corrosion of Pipeline Steel under Disbonded Coating. Corrosion Science, 2009. 51 pp. 2242-2245. 9. Perdomo, J. J., Chabica, M. E., and Song, I. Chemical and Electrochemical Conditions on Steel under Disbonded Coatings: the Effect of Previously Corroded Surfaces and Wet and Dry Cycles. Corrosion Science, 2001. 43 pp. 515-532. 10. Eslami, A., Fang, B., Kania, R., Worthingham, B., Been, J., Eadie, R., and Chen, W. Stress Corrosion

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Cracking Initiation under the Disbonded Coating of Pipeline Steel in Near-neutral pH Environment. Corrosion Science, 2010. 52 pp. 3750-3756. Been, J., King, F., Yang, L., Song, F., and Sridhar. N. The Role of Coatings in the Generation of High- and Near-neutral pH Environments that Promote Environmentally Assisted Cracking. Corrosion, 2005. NACE International, Houston, TX: Paper 05167. Chen, X., Du, C., Li, X., and Huang, Y. Effects of Cathodic Potential on the Local Electrochemical Environment under a Disbonded Coating. Journal of Applied Electrochemistry, 2009. 39, pp. 697-704. Chen, W., and Sutherby, R. L. Crack Growth Behavior of Pipeline Steel in Near-neutral PH Soil Environments. Metallurgical & Material Transections A, 2007. 38A, pp. 1260-1268. Zhang, L., Li, X. G., Du, C. W., and Cheng, Y.F. Corrosion and Stress Corrosion Cracking Behavior of X70 Pipeline Steel in a CO2-containing Solution. Journal of Materials Engineering and Performance, 2009. 18, pp. 319-323. Nei. S. Carbon Dioxide Corrosion of Mild Steel.Uhligs Corrosion Handbook (3rd Edition), 2011. John Wiley & Sons, Hoboken, New Jersey, pp. 229.


Element C Mn P S Si Cu Ni Cr Mo V Nb Ti Al Sn Ca B Pb Zr Co

Composition, wt% 0.12 1.5 0.017 0.0046 0.26 0.014 <0.02 0.065 <0.03 <0.01 0.049 <0.005 0.029 0.0016 0.0012 <0.0005 <0.01 <0.002 0.004


Component MgSO4*7H2O CaCl2 KCl NaHCO3 CaCO3

Concentration (g/L) 0.0274 0.0255 0.0035 0.0195 0.0606


Component H2O Cis-2-butene-1,4-diol HCl

Concentration (g/L) 100 4 3

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